EP0407871A1 - Water soluble disazo compounds, process for their preparation and their use as dyestuffs - Google Patents

Abstract

Water-soluble disazo compounds having fibre-reactive dye properties and capable of dyeing carboxamido- and/or hydroxyl-containing materials, in particular fibre materials, such as synthetic polyamide, wool and in particular cellulose fibre materials, in strong fast shades. They conform to the general formula (1) <IMAGE> where D<1> is a phenylene radical which may be substituted by 1 or 2 substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, carboxyl and sulpho or is a naphthylene radical which may be substituted by a sulfo group; R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms which may be substituted by 1 or 2 substituents selected from the group consisting of hydroxyl, sulpho, carboxyl, sulphato and phosphato; Y<1> is vinyl or an ethyl group which contains in the beta -position a substituent which is eliminable by means of alkali to form a vinyl group; M is a hydrogen atom or an alkali metal; D<2> is a group of the general formula (2a), (2b) or (2c) <IMAGE> where R<1> is a hydrogen atom, cyano, an alkyl group of 1 to 4 carbon atoms or a sulpho-, carboxyl- or sulphato-substituted alkyl group of 1 to 4 carbon atoms or a hydroxyl group, an alkoxy group of 1 to 4 carbon atoms or a sulpho-, carboxyl- or sulphato-substituted alkoxy group of 1 to 4 carbon atoms or a sulpho or carboxyl group or a halogen atom, Y is vinyl or an ethyl group which contains in the beta -position a substituent which is eliminable by means of alkali to form a vinyl group, n is zero or 1 (if zero, this group being hydrogen) and M is as defined above.

Description

The invention is in the technical field of fiber-reactive dyes.

Fiber-reactive disazo compounds with dye properties, which, for example, can dye cellulose fiber materials in navy blue tones, are known, for example, from European patent application publications Nos. 0 133 283A, 0 174 909A and 0 282 443A. However, increasing demands on the quality of the dyeings and on the economy of the dyeing process have made it necessary to develop improved dyes. Because especially for dyeing cellulosic fiber materials, such as cotton, using the block-cold retention process, dyes are required which are readily soluble and which are highly reactive at the low dyeing and fixing temperatures. They should have a high degree of fixation so that they can be used economically and ecologically with great advantage in the dyeing processes. In addition, the dyes are said to provide dyeings with good fastness properties, such as, for example, good wet fastness and light fastness.

This object has been achieved with the invention described below.

in welcher bedeuten:
D¹ ist ein Phenylenrest, der durch 1 oder 2 Substituenten aus der Gruppe Alkyl von 1 bis 4 C-Atomen, wie Methyl, Alkoxy von 1 bis 4 C-Atomen, wie Methoxy und Ethoxy, Chlor, Carboxy und Sulfo substituiert sein kann, oder ist ein Naphthylenrest, wobei an den Naphthylenrest die Azogruppe bevorzugt in 1- oder 2-Stellung und die Ureidogruppierung bevorzugt in 4-Stellung gebunden ist und der Naphthylenrest durch eine Sulfogruppe substituiert sein kann;
R ist ein Wasserstoffatom oder eine Alkylgruppe von 1 bis 4 C-Atomen, wie die Methyl- oder Ethylgruppe, die durch 1 oder 2, bevorzugt 1, Substituenten aus der Gruppe Hydroxy, Sulfo, Carboxy, Sulfato und Phosphato substituiert sein kann, bevorzugt jedoch die Methylgruppe und insbesondere ein Wasserstoffatom;
Y¹ ist die Vinylgruppe oder eine Ethylgruppe, die in β-Stellung einen Substituenten enthält, der durch Alkali unter Bildung der Vinylgruppe eliminierbar ist;
M ist ein Wasserstoffatom oder ein Alkalimetall, wie Natrium, Kalium und Lithium;
D² ist eine Gruppe der allgemeinen Formel (2a), (2b) oder (2c)

in welchen
R¹ ein Wasserstoffatom, die Cyangruppe, eine Alkylgruppe von 1 bis 4 C-Atomen, wie die Methyl- oder Ethylgruppe, ist, oder eine durch eine Sulfo-, Carboxy- oder Sulfatogruppe substituierte Alkylgruppe von 1 bis 4 C-Atomen oder eine Hydroxygruppe, eine Alkoxygruppe von 1 bis 4 C-Atomen, wie die Methoxy- oder Ethoxygruppe, oder eine durch eine Sulfo-, Carboxy- oder Sulfatogruppe substituierte Alkoxygruppe von 1 bis 4 C-Atomen oder eine Sulfo- oder Carboxygruppe oder ein Halogenatom, wie ein Brom- oder Chloratom, ist,
Y die Vinylgruppe oder eine Ethylgruppe ist, die in β-Stellung einen Substituenten enthält, der durch Alkali unter Bildung der Vinylgruppe eliminierbar ist,
n für die Zahl Null oder 1 steht (wobei im Falle von n gleich Null diese Gruppe ein Wasserstoffatom bedeutet) und
M die obengenannte Bedeutung besitzt.The invention relates to water-soluble disazo compounds corresponding to the general formula (1)

in which mean:
D 1 is a phenylene radical which can be substituted by 1 or 2 substituents from the group alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, chlorine, carboxy and sulfo, or is a naphthylene radical, where the azo group is preferably bonded to the naphthylene radical in the 1- or 2-position and the ureido group is preferably bound in the 4-position and the naphthylene radical can be substituted by a sulfo group;
R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as the methyl or ethyl group, which can be substituted by 1 or 2, preferably 1, substituents from the group hydroxyl, sulfo, carboxy, sulfato and phosphato, but is preferred the methyl group and especially a hydrogen atom;
Y¹ is the vinyl group or an ethyl group which contains a substituent in the β-position which can be eliminated by alkali to form the vinyl group;
M is a hydrogen atom or an alkali metal such as sodium, potassium and lithium;
D² is a group of the general formula (2a), (2b) or (2c)

in which
R¹ is a hydrogen atom, the cyano group, an alkyl group of 1 to 4 carbon atoms, such as the methyl or Is ethyl group, or an alkyl group of 1 to 4 carbon atoms substituted by a sulfo, carboxy or sulfato group or a hydroxy group, an alkoxy group of 1 to 4 carbon atoms, such as the methoxy or ethoxy group, or one by a sulfo -, carboxy or sulfato group substituted alkoxy group of 1 to 4 carbon atoms or a sulfo or carboxy group or a halogen atom, such as a bromine or chlorine atom,
Y is the vinyl group or an ethyl group which contains a substituent in the β-position which can be eliminated by alkali to form the vinyl group,
n stands for the number zero or 1 (where, if n is zero, this group denotes a hydrogen atom) and
M has the meaning given above.

The individual formula members of the general formula (1) can have meanings which are identical to or different from one another.

Particularly preferred in formula (1) D 1 is the 1,3- or 1,4-phenylene group, which may be substituted by a carboxy or preferably 1 or 2, preferably 1, sulfo groups.

R 1 is preferably the methyl, methoxy, ethoxy, carboxy or sulfo group and particularly preferably a hydrogen atom. In the formula radical (2a) the group -SO₂-Y is preferably in the meta and in particular in the para position to the free bond connected to the azo group.

Alkaline eliminable substituents which are in the β-position of the ethyl group of the formula members Y 1 and Y are for example alkanoyloxy groups of 2 to 5 carbon atoms, such as the acetyloxy group, aroyloxy groups, such as the benzoyloxy, sulfobenzoyloxy or carboxybenzoyloxy group, the alkylamino groups with alkyl radicals of 1 to 4 carbon atoms, such as, in particular, the dimethylamino and diethylamino group, trialkylammonium groups Alkyl radicals with 1 to 4 carbon atoms, such as the trimethylammonium group, the chlorine atom, the bromine atom, alkylsulfonyloxy groups of 1 to 4 carbon atoms, such as the methylsulfonyloxy group, and in particular a phosphato, thiosulfato and sulfato group. Y and Y 1 are preferably, independently of one another, the vinyl group, the β-chloroethyl, β-thiosulfatoethyl and the β-sulfatoethyl group. In particular, Y is preferably the β-sulfatoethyl group and Y 1 is the β-chloroethyl, β-sulfatoethyl or β-thiosulfatoethyl group.

entsprechen, in welchen M, Y¹ und Y die obengenannten, insbesondere bevorzugten Bedeutungen haben.Of the disazo compounds of the general formula (1) according to the invention, those which have the general formula (1a)

correspond in which M, Y 1 and Y have the above-mentioned, particularly preferred meanings.

The "sulfo", "carboxy", "phosphato", "thiosulfato" and "sulfato" substituents include both their acid form and their salt form. Accordingly, sulfo groups mean groups corresponding to the general formula -SO₃M, carboxy groups corresponding to the general formula Formula -COOM, phosphato groups according to the general formula -OPO₃M₂, thiosulfato groups according to the general formula -S-SO₃M and sulfato groups according to the general formula -OSO₃M, each with M of the meaning given above.

- D¹ - NH₂      (3)
in welcher Y¹, R und D¹ die obengenannten Bedeutungen haben, diazotiert und mit einer Verbindung der allgemeinen Formel (4)

in welcher M und D² die obengenannten Bedeutungen haben, kuppelt,
oder daß man eine Verbindung der allgemeinen Formel (5)

in welcher R, D¹, M und D² die obengenannten Bedeutungen haben, mit einer Isocyanatverbindung der allgemeinen Formel (6)
Y¹ - SO₂ - (CH₂)₃ - NCO      (6)
in welcher Y¹ die obengennante Bedeutung besitzt, umsetzt.The present invention further relates to processes for the preparation of the disazo compounds of the general formula (1). They are characterized in that a compound of the general formula (3)

Y¹ - SO₂ - (CH₂) ₃ - NH - CO -

- D¹ - NH₂ (3)
in which Y¹, R and D¹ have the meanings given above, diazotized and with a compound of the general formula (4)

in which M and D² have the meanings given above,
or that a compound of the general formula (5)

in which R, D¹, M and D² have the meanings given above, with an isocyanate compound of the general formula (6)
Y¹ - SO₂ - (CH₂) ₃ - NCO (6)
in which Y¹ has the meaning given above.

The diazotization and coupling reaction according to the invention is carried out analogously to known methods of diazotization and coupling, in particular in an aqueous medium, the diazotization, for example, using nitrous acid (for example using sodium nitrite in aqueous mineral acid, such as hydrochloric or sulfuric acid solution) at a temperature of -5 ° C to + 15 ° C and at a pH below 2 and the coupling reaction, for example at a temperature between 5 and 40 ° C, preferably between 10 and 25 ° C, and at a pH between 3, 5 and 7.5, preferably between 4 and 7, is carried out.

The inventive reaction of the amino disazo compound of the general formula (5) with the isocyanate of the general formula (6) is also carried out analogously to generally known process conditions, as described for the reaction of amino compounds with isocyanates (see Houben-Weyl, Methods of Organic Chemistry, volume 8 (1952), pages 149-163, G. Thieme-Verlag, Stuttgart, and its 4th supplement (1983), pages 334-342 and 352-357). In particular, the reaction according to the invention takes place in such a way that a solution of the isocyanate of the general formula (6) with Y 1 of the abovementioned meaning, where Y 1 is preferably β-chloroethyl, in an organic solvent, preferably chlorobenzene, with an aqueous solution of the compound ( 5) while maintaining a pH between 5 and 9 and a temperature between 0 and 70 ° C, preferably between 15 and 30 ° C, stirred together or brought together for reaction in another, conventional way.

The starting compounds corresponding to the general formula (3) can be prepared in accordance with known procedures (Houben-Weyl, loc. Cit.) By reacting an amine of the general formula HN (R) -D¹-NH₂ with R and D¹ as defined above with an isocyanate of the general formula (6) in which Y¹ is the above Has meaning, preferably is β-chloroethyl, produce. The starting compounds of the general formula (6) are also obtained analogously to known procedures by reacting an amine of the formula H₂N- (CH₂) ₃-SO₂-Y¹ with Y¹ of the above meaning, such as, for example, γ- (β'-chloroethylsulfonyl) propylamine, which is known from German Offenlegungsschrift No. 2 040 620, with phosgene.

The starting compounds of the general formulas (4) and (5) are described in numerous numbers in the patent literature. They can be, for example, by coupling 3,6-disulfo-1-amino-8-naphthol in a strongly acidic medium with the diazonium salt of the amine of the formula D²-NH₂ and, if appropriate, subsequent coupling reaction with the diazonium salt of the amine of the formula HN (R) - D¹-NH₂ in the weakly acidic to neutral, optionally to weakly alkaline, produce range.

Starting compounds of the general formula HN (R) -D¹-NH₂ are, for example, 4-sulfo-1,3-diaminobenzene, 2-sulfo-1,4-diaminobenzene, 2,5-disulfo-1,4-diaminobenzene, 4,6- Disulfo-1,3-diaminobenzene, 4-carboxy-1,3-diaminobenzene and 4-methyl-1,3-diaminobenzene.

Starting compounds of the general formula D²-NH₂ are, for example, 4- (β-sulfatoethylsulfonyl) aniline, 3- (β-sulfatoethylsulfonyl) aniline, 4- (β-thiosulfatoethylsulfonyl) aniline, 8- (β-sulfatoethylsulfonyl) -6-sulfo -2-aminonaphthalene and 6- (β-sulfatoethylsulfonyl) -8-sulfo-2-aminonaphthalene.

Both the disazo compounds according to the invention of the general formula (1) and the starting compounds of the general formula (3) used according to the invention can, with regard to their fiber-reactive radicals -SO₂-Y or -SO₂-Y¹, in analogy to known procedures in compounds with otherwise the same constitution, however with a group in which Y and Y¹ represent another group, for example, starting from the compounds having a β-sulfatoethylsulfonyl or β-chloroethylsulfonyl group into those in which Y and Y¹ are vinyl groups, and starting of compounds with the β-chloroethylsulfonyl or the vinylsulfonyl group into those in which Y and Y¹ are the β-thiosulfatoethylsulfonyl group. For example, the vinylsulfonyl compounds can be derived from their corresponding β-chloroethylsulfonyl compounds or their compounds in which Y or Y¹ is the ethyl group which, in the β-position, contains the ester group of an organic or inorganic acid as a substituent, such as, for example, the sulfato or the acetyloxy group, in such a way that an alkali in aqueous medium at a pH between 10 and 12 and at a temperature between 20 and 50 ° C, depending on the temperature, for 10 minutes to 3 hours on these compounds can act, for example at a temperature of 50 ° C for 10 to 20 minutes or at a temperature of 25 ° C for two to three hours, and from the β-chloroethylsulfonyl compound or the vinylsulfonyl compound can be at a pH -Value between 4 and 9 and a temperature between 20 and 60 ° C by reaction with sodium thiosulfate the corresponding β-thiosulfatoethylsulfonyl-Ve Make a bond.

The separation and isolation of the disazo compounds of the general formula (1) prepared according to the invention from the synthesis solutions can be carried out by generally known methods, for example either by precipitation from the reaction medium by means of electrolytes, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution, for example spray drying. a buffer substance can be added to the synthesis solution.

The disazo compounds according to the invention of the general formula (1) - hereinafter called compounds (1) - have fiber-reactive properties and very good dye properties. They can therefore be used for dyeing (including printing) fiber materials containing hydroxyl groups and / or carbonamide groups. The solutions obtained in the synthesis of the compounds (1), if appropriate after adding a buffer substance and if appropriate also after concentration, can also be used directly as a liquid preparation for dyeing.

The present invention therefore also relates to the use of the compounds (1) according to the invention for dyeing (including printing) fiber materials containing hydroxyl and / or carbonamide groups and processes for their use on these substrates. This can be done analogously to known procedures.

Materials containing hydroxyl groups are of natural or synthetic origin, such as cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; Regenerated cellulose fibers are, for example, cellulose and viscose rayon.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The compounds (1) can, according to the application according to the invention, on the substrates mentioned apply and fix according to the application techniques known for water-soluble dyes, in particular fiber-reactive dyes, for example by applying the compound (1) in dissolved form to the substrate or introducing it therein and placing it on or in the substrate, possibly by exposure to heat and / or fixed by the action of an alkaline agent. Such staining and fixing methods have been described in numerous technical and patent literature, for example in European Patent Application Publication No. 0 181 585A. Because of their good water solubility, they are also particularly suitable for the block-cold retention process.

With the compounds (1), both navy blue dyeings and prints with good fastness properties, such as good pleating, ironing and rubbing fastness and in particular good light fastness, are used both on materials containing carbonamide groups, such as in particular on wool, and on material containing hydroxyl groups, such as in particular cellulose fiber material good wet fastness properties, from which in particular the sweat fastness can be emphasized.

The following examples serve to illustrate the invention. The parts are parts by weight, the percentages represent percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

The compounds described by formula in these examples are given in the form of the free acids; in general, they are prepared and isolated in the form of their sodium or potassium salts and used for dyeing in the form of their salts. Likewise, those in the following Examples in the form of the free acid starting compounds and components as such or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts, are used in the synthesis.
The absorption maximum indicated in the visible range (λ _max value) was determined from an aqueous solution of the alkali metal salt.

Example A

In a heated to 100 ° C suspension of 111 parts of γ- (β'-chloroethylsulfonyl) propylamine hydrochloride in 500 parts by volume of chlorobenzene, 125 parts of phosgene are introduced within 6 to 8 hours. The mixture is stirred for a further two hours and then excess phosgene is removed by blowing out with nitrogen. A slightly yellowish solution of γ- (β'-chloroethylsulfonyl) propyl isocyanate is obtained, which can be used directly as a starting compound for the synthesis of the disazo compounds according to the invention.

The γ- (β'-chloroethylsulfonyl) propyl isocyanate has not yet been described in the literature. It has an NCO band at 2282 cm bei¹ in the IR spectrum. A small part of the isocyanate solution can be stirred with aniline for characterization. After a short time, the N- [γ- (β′-chloroethylsulfonyl) propyl] -N′-phenylurea separates, which, after recrystallization from ethanol, has a melting point of 140 ° to 142 ° C.
The elementary analysis showed the following values:
calc .: C 47.3%, H 5.6%, N 9.2%, S 10.5%,
Found: C 47.6%, H 5.7%, N 9.3%, S 9.8%.
The structure was also confirmed by NMR spectroscopy.

Example B

220 parts of an aqueous solution of 19 parts of 4-sulfo-1,3-diaminobenzene are mixed with a quarter of the isocyanate solution prepared in Example A at a pH of 4.5 and a temperature of 20 to 25 ° C. with vigorous stirring. The reaction is complete after a reaction time of four to five hours. The organic phase is separated off. To characterize the ureido compound produced, part of the aqueous phase can be removed; he is adjusted to a pH of 1.5, stirred for a few hours, and the separated compound N- [γ- (β'-chloroethylsulfonyl) propyl] -N'- (3-amino-4-sulfophenyl) urea is isolated. Your structure has been through 1 H-NMR spectroscopy and confirmed by elemental analysis.

Elemental analysis:
calc .: C 36.0%, H 4.5%, N 10.5%, Cl 8.9%,
Found: C 35.9%, H 4.6%, N 10.1%, Cl 9.2%.

example 1

To prepare a disazo compound according to the invention, 20 parts of an aqueous 5N sodium nitrite solution are added to the aqueous solution of the urea compound prepared in Example B and the mixture is slowly poured into a mixture of 200 parts of ice, 100 parts of water and 40 parts of an aqueous concentrated hydrochloric acid with thorough stirring . The diazotization reaction is complete after about 2 hours. Then 58 parts of the compound 2- [4 ′ - (β-sulfatoethylsulfonyl) phenylazo] -3,6-disulfo-1-amino-8-naphthol are added and the coupling reaction is carried out at a pH of 4.5 and at a temperature of 20 ° C.

entspricht, in welcher die Sulfogruppe im Benzolrest vorwiegend in ortho-Stellung zur Azogruppe gebunden steht (bei der Umsetzung der Isocyanatausgangsverbindung wird teilweise das Isomere Harnstoffderivat gebildet), wird aus der zuvor geklärten Syntheselösung durch Eindampfen oder durch Sprühtrocknung als Alkalimetallsalz (Natriumsalz) isoliert.The disazo compound of the invention obtained, which (written in the form of the free acid) of the formula

in which the sulfo group in the benzene radical is predominantly bound in the ortho position to the azo group (the isomer urea derivative is partially formed in the reaction of the isocyanate starting compound), is isolated from the previously clarified synthesis solution by evaporation or by spray drying as an alkali metal salt (sodium salt).

The disazo compound according to the invention has very good fiber-reactive dye properties and, on the materials mentioned in the description, such as, in particular, cellulose fiber materials, supplies navy-blue dyeings and prints with good fastness properties, of which in particular the good light, in accordance with the application and fixing processes customary in the art for fiber-reactive dyes. , Wet light and wash fastness can be highlighted. The disazo compound according to the invention is distinguished by a high degree of fixation.

Example 2

das sehr gute faserreaktive Farbstoffeigenschaften besitzt und marineblaue Färbungen und Drucke mit hohem Fixiergrad mit den für die erfindungsgemäße Disazoverbindung des Beispieles 1 angegebenen guten Echtheitseigenschaften liefert.To prepare a disazo compound according to the invention, the procedure of Example 1 is followed, but the starting compound 2-sulfo-1,3-diaminobenzene used there is replaced by the same amount of 2-sulfo-1,4-diaminobenzene. The alkali metal salt of the compound is obtained according to the formula

which has very good fiber-reactive dye properties and provides navy blue dyeings and prints with a high degree of fixation with the good fastness properties indicated for the disazo compound according to the invention of Example 1

Claims (16)

1. Process for the preparation of a disazo compound according to the general formula (1)

in which mean:
D 1 is a phenylene radical which may be substituted by 1 or 2 substituents from the group alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, carboxy and sulfo, or is a naphthylene radical which is substituted by a sulfo group can be substituted
R is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, which can be substituted by 1 or 2 substituents from the group consisting of hydroxyl, sulfo, carboxy, sulfato and phosphato;
Y¹ is the vinyl group or an ethyl group which contains a substituent in the β-position which can be eliminated by alkali to form the vinyl group;
M is a hydrogen atom or an alkali metal;
D² is a group of the general formula (2a), (2b) or (2c)

in which
R¹ is a hydrogen atom, the cyano group, an alkyl group of 1 to 4 carbon atoms or an alkyl group of 1 to 4 carbon atoms substituted by a sulfo, carboxy or sulfato group or a hydroxy group, an alkoxy group of 1 to 4 carbon atoms or is an alkoxy group of 1 to 4 carbon atoms substituted by a sulfo, carboxy or sulfato group or a sulfo or carboxy group or a halogen atom,
Y is the vinyl group or an ethyl group which contains a substituent in the β-position which can be eliminated by alkali to form the vinyl group,
n stands for the number zero or 1 (where, if n is zero, this group denotes a hydrogen atom) and
M has the abovementioned meaning, characterized in that a compound of the general formula (3)

Y¹ - SO₂ - (CH₂) ₃ - NH- CO -

-D¹ - NH₂ (3)
in which Y¹, R and D¹ have the meanings given above, diazotized and with a compound of the general formula (4)

in which M and D² have the meanings given above,
or that a compound of the general formula (5)

in which R, D¹, H and D² have the meanings given above, with an isocyanate compound of the general formula (6)
Y¹ - SO₂ - (CH₂) ₃ - NCO (6)
in which Y¹ has the meaning given in claim 1. 2. The method according to claim 1, characterized in that R is a hydrogen atom or the methyl group. 3. The method according to claim 1 or 2, characterized in that D¹ is the 1,3- or 1,4-phenylene group, which can be substituted by a carboxy group or by 1 or 2 sulfo groups. 4. The method according to at least one of claims 1 to 3, characterized in that D² is a group of the general formula (2a)

with R¹ and Y is as defined in claim 1. 5. The method according to claim 4, characterized in that R¹ is the methyl, methoxy, ethoxy, carboxy or sulfo group. 6. The method according to claim 4, characterized in that R¹ is a hydrogen atom. 7. The method according to at least one of claims 1 to 6, characterized in that the group -SO₂-Y in formula (2a) is bound in the meta or para position for free binding to the benzene nucleus. 8. The method according to at least one of claims 1 to 7, characterized in that Y and Y¹ each independently represent the vinyl group, the β-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl group. 9. The method according to at least one of claims 1 to 7, characterized in that Y¹ is the β-chloroethyl, β-sulfatoethyl or β-thiosulfatoethyl group. 10.The method according to at least one of claims 1 to 7 and 9, characterized in that Y is the β-sulfatoethyl group. 11. The method according to claim 1, characterized in that the compound of formula (1) is a compound according to general formula (1a)

is in which M, Y¹ and Y have the meanings given in claim 1. 12. The method according to claim 11, characterized in that Y¹ is the β-chloroethyl, β-sulfatoethyl or β-thiosulfatoethyl group. 13. The method according to claim 11 or 12, characterized in that Y is the β-sulfatoethyl group. 14. Use of a dye of at least one of claims 1 to 13 for dyeing and printing material containing hydroxyl and / or carbonamide groups, in particular fiber material. 15. A process for dyeing and printing material containing hydroxyl and / or carbonamide groups, preferably fiber material, in which a dye is applied to or introduced into the material and the dye is applied to or in the material by means of heat or with the aid of an alkaline agent or fixed by means of heat and with the aid of an alkaline agent, characterized in that a dye of at least one of claims 1 to 13 is used as the dye.